CN106637282B - A kind of method of cyclization - Google Patents
A kind of method of cyclization Download PDFInfo
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- CN106637282B CN106637282B CN201610887772.0A CN201610887772A CN106637282B CN 106637282 B CN106637282 B CN 106637282B CN 201610887772 A CN201610887772 A CN 201610887772A CN 106637282 B CN106637282 B CN 106637282B
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000007363 ring formation reaction Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- PRMAVUPVLGOONQ-JOWSBRCASA-N (3e,5e)-3,6,10-trimethylundeca-3,5,9-trien-2-one Chemical compound CC(C)=CCC\C(C)=C\C=C(/C)C(C)=O PRMAVUPVLGOONQ-JOWSBRCASA-N 0.000 claims abstract description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 26
- 238000005868 electrolysis reaction Methods 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000036647 reaction Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 5
- JRJBVWJSTHECJK-PKNBQFBNSA-N 3-Methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one Chemical compound CC(=O)C(\C)=C\C1C(C)=CCCC1(C)C JRJBVWJSTHECJK-PKNBQFBNSA-N 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000012043 crude product Substances 0.000 description 15
- VPKMGDRERYMTJX-CMDGGOBGSA-N 1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-penten-3-one Chemical compound CCC(=O)\C=C\C1C(C)=CCCC1(C)C VPKMGDRERYMTJX-CMDGGOBGSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 229930183419 Irisone Natural products 0.000 description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229930002839 ionone Natural products 0.000 description 5
- 150000002499 ionone derivatives Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- -1 methyl irisone Chemical compound 0.000 description 4
- 229960001124 trientine Drugs 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- ZGCJYCWVWYQKEE-UHFFFAOYSA-N 1,1-difluoro-3-methylcyclohexane Chemical class CC1CCCC(F)(F)C1 ZGCJYCWVWYQKEE-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- WVRADMCUPTUOJE-UHFFFAOYSA-N 1-fluoro-2-methylcyclohexane Chemical class CC1CCCCC1F WVRADMCUPTUOJE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- NSSHGPBKKVJJMM-PKNBQFBNSA-N delta-Methylionone Chemical compound CC(=O)C(\C)=C\C1=C(C)CCCC1(C)C NSSHGPBKKVJJMM-PKNBQFBNSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of cyclization, is specifically method of the compound shown in formula (I) by compound shown in electrolytic preparation formula (II)：
Description
Technical field
The present invention relates to the method for cyclization, belong to organic synthesis field, more particularly relate to prepare by electrochemical method
The method of α-daphnone and its derivative.
Background technology
Methylionone is the homologue of irisone, but the taste of its fragrance is more excellent than irisone, its grace is soft
Note and good stability deeply favored by people.It has 6 kinds of isomers, be respectively α-daphnone (α-
ISO), β-isomethylionone (β-ISO), γ-isomethylionone (γ-ISO), α-positive methylionone (α-N),
β-positive methylionone (β-N) and γ-positive methylionone (γ-N), wherein again the purest happy with the fragrance of α-ISO
People, the price of commercially available methylionone spices is raised also with the rise of α-ISO content of isomer, as α-ISO contents are
Price of 90% price apparently higher than the product that content is 60%.
Existing electrochemical techniques relate generally to following several reaction types.
In electrofluorination field,《Preparation of Perfluoro Tributylamine by Electrolytical Fluorination is studied》(В А horses Tallin《Chemical Manufacture and skill
Art》, 2006.13 (3) 4-5) described in, it is mixture that it, which generates product, and the recovery rate of purpose compound is not high.It is secondary to decompose fluorination
The consumed electric current of reaction increases with increasing for carbon atom in original chemical.Oily compound aggregation is generated in electrolytic process
In the electrolytic solution, adhere on the electrode, it is difficult to continuous long-term electrolysis.
In acrylonitrile electrolysis adiponitrile field,《Electrolytic Dimeric Acrylonitrile produces adiponitrile》(apply Jinchang《Synthetic fibre maker
Industry》, 1986 (1)) described in, it happens is that Electrolytic Oxidative Coupling Process reacts, and the three wastes are more, and processing cost is high.
Producing benzaldehyde field is being electrolysed,《The new development of benzaldehyde electro synthesis technology》(Li Yanwei《Modern industry》,
2006.26(1)：Described in 15-19), using indirect electrosynthesis method synthesizing benzaldehyde, process is the presence in supporting electrolyte
Under, electronics electroxidation electrolytic medium first, the electrolytic medium aoxidized deoxidation organic matter again, then electrolytic medium is again logical in itself
Cross the activity that electrolysis recovers its original.
In chlorine industry, saturation NaCl is electrolysed, produces hydrogen in anode, anode produces NaOH and hydrogen, main to occur
Be redox reaction.
Existing electrochemical techniques reaction type is mostly redox reaction above, and target product yield is relatively low.
There is the synthetic route of a variety of methylionones in the prior art, but it is insufficient.
《The synthesis of methylionone》(Tang Jian《Coal and chemical industry》, 2011.34 (2), 56-58) disclose and made with toluene
For solvent, cyclizing agent is made using acid such as phosphoric acid, makes X-ray computed that cyclization, synthesizing methyl irisone occur.
Become positive methylionone after the false positive Methyl Ionone by Cyclization Reaction of this method, become different after pseudoisomethyl ionone cyclisation
Methylionone.Again because of the displacement of double bond, can produce α-, β -- and γ-isomers, so product is generally 6 kinds of isomers
Mixture.Have a great influence, be not readily separated to product quality.
《With immobilized strong acid TiO2/SO4 2-The cyclization being catalyzed in methylionone synthesis》(Cui Zhimin《Chemistry is logical
Report》, 2002,65 (2)：130-134) disclose with immobilized strong acid TiO2/SO4 2-Catalyst is made, solvent is made with dimethylbenzene, makes vacation
Property methylionone occur cyclization, synthesizing methyl irisone.This method catalyst preparation is complicated, and purity is relatively low, generally
77% or so.
Methylionone is at present raw material by citral and butanone, is made through being condensed, being cyclized two-step reaction, wherein α-
ISO content of isomer is up to 60%, needs rectification and purification to obtain the product of 90% content.
Current technique is faced with following problem：1) complex process, equipment investment are big；2) it is more that the three wastes are produced；3) selectivity
Difference, beta isomer is more, and fragrance is unsatisfactory.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of method of cyclization.By using electrochemistry
Technique, the high selectivity of α-daphnone product, high-purity, in high yield are realized by non-oxide reduction reaction.Afterwards
In processing procedure, the direct circulation for realizing solvent except solvent by flashing is applied mechanically.After rectifying, α-daphnone content
More than 99%, product yield 99%.
The present invention uses following technical scheme：
The present invention provides the method that compound shown in a kind of formula (I) passes through compound shown in electrolytic preparation formula (II)：
R1、R2、R3、R4Mutually independent expression H, halogen, aryl, C1~C6Straight or branched alkyl, C3~C6Cycloalkyl；
R5Selected from H or cyclopropyl；Preferable R1、R2、R3、R4Mutually independent expression methyl, F.
The method of the invention comprises the following steps：1) take compound shown in a certain amount of formula (I), using organic solvent and
H2O is as electrolyte, and be powered electrolysis；2) electrolyte is carried out flashing to obtain crude compound and electrolyte shown in formula (II)；3) formula
(II) crude compound rectifying shown in separates to obtain compound products shown in formula (II).
The temperature of electrolysis of the present invention is 10 DEG C~30 DEG C, preferably 18 DEG C~22 DEG C.
Electrode potential of the present invention is 5V~25V, preferably 12V~18V.
The cell reaction time of the present invention is 1~3h, preferably 1.4~1.6h.
Cathode of electrolytic tank of the present invention is carbon-point, and the anode is Cu, Ag or Pt, preferably Pt.
Organic solvent of the present invention is selected from dioxane or tetrahydrofuran.
Compound shown in formula (I) of the present invention：Organic solvent：H2The mass ratio of O is (2~6)：(2~4)：(1~3).
Preferably, the example of compound shown in formula (I) of the present invention have pseudoisomethyl ionone, (3E, 6Z)-
10,10- bis- fluoro- 3,6- dimethyl -3,6,9- trien -2- ketone, (3E, 6Z) -8- cyclopropyl -3,6,10- trimethyls -
3,6,9- trien -2- ketone.
Pseudoisomethyl ionone
Fluoro- 3, the 6- dimethyl -3,6 of (3E, 6Z) -10,10- bis-, 9- trien -2- ketone
(3E, 6Z) -8- cyclopropyl -3,6,10- trimethyls -3,6,9- trien -2- ketone
The present invention also provides a kind of preparation method of α-daphnone, comprise the following steps：False different crystal violet
Rowland ketone passes through electrolytically generated α-daphnone.
A kind of preparation method of α-daphnone, comprises the following steps：1) a certain amount of false different crystal violet sieve is taken
Blue ketone, uses organic solvent and H2O is as electrolyte, and be powered electrolysis；2) electrolyte is carried out flashing to obtain α-different methyl violet
Ketone crude product and electrolyte；3) rectifying of α-daphnone crude product separates to obtain α-daphnoneProduct.
The electrolysis temperature of the present invention for preparing α-daphnone be 10 DEG C~30 DEG C, preferably 18 DEG C~22
℃。
The electrode potential of the present invention for preparing α-daphnone is 5V~25V, preferably 12V~18V.
The cell reaction time of the present invention for preparing α-daphnone is 1~3h, preferably 1.4~1.6h.
The cathode of electrolytic tank of the present invention for preparing α-daphnone is carbon-point, the anode for Cu, Ag or
Pt, preferably Pt.
The organic solvent of the present invention for preparing α-daphnone is selected from dioxane or tetrahydrofuran.
Pseudoisomethyl ionone of the present invention：Organic solvent：H2The mass ratio of O is (2~6)：(2~4)：(1~
3)。
By taking the synthesis of α-daphnone as an example, illustrate reaction mechanism.
Cathode reaction：
Anode reaction：
Compared with prior art, present invention reaction carries out at 10 DEG C~30 DEG C and reaction process is easily controllable, technique ring
Border pollution is small, and the electrolyte flashed can reuse, and α-daphnone is selectively more than 99%, yield and is more than
99%, product purity is more than 98%, and process is simple, is conducive to industrialized production, environmentally protective.This fragrance aroma is pure, has
Strong violet characteristic perfume.
Embodiment
Nuclear-magnetism：Bruker AV400
Mass spectrum：Equipment and vendor name Agilent 5975E
Gas chromatography analysis method：Shimadzu gas-chromatography 2010；Chromatographic column Agilent DB-5
Post case temperature：100℃；Injector temperature：280℃；Split ratio 10:1；Carrier gas flux：1mL/min；
Heating schedule：0min is kept at 100 DEG C, 120 DEG C is risen to the speed of 5 DEG C/min, continues with the speed of 20 DEG C/min
Rate rises to 200 DEG C, keeps 7min.
Embodiment 1
100kg water and 150kg dioxane are added in 800L electrolytic cells, electrolytic cell anode Pt, cathode is carbon-point.
After opening stirring, 100kg pseudoisomethyl ionones are added into electrolytic cell.5V voltages, maintenance system 10 are passed through to electrode
1.5h is reacted at DEG C.Electrolyte flashes at 20kPa, 55 DEG C, and residence time 0.5min, obtains α-daphnone crude product
110kg and dioxane aqueous solution 230kg, dioxane aqueous solution directly apply mechanically back reaction kettle.α-daphnone is thick
Product rectifying at 1.4kPa, 120 DEG C, reflux ratio 3, obtains α-daphnone fine work 99kg.Gas chromatographic analysis selects
Property 99.1%, yield 99%, purity 98.9%.
Embodiment 2
The dioxane aqueous solution recycled in embodiment 1 and 70kg water are added in 800L electrolytic cells, electrolytic cell anode
For Pt, cathode is carbon-point.After opening stirring, 100kg pseudoisomethyl ionones are added into electrolytic cell.It is passed through to electrode
10V voltages, react 1h at 20 DEG C of maintenance system.Electrolyte flashes at 25kPa, 60 DEG C, residence time 0.5min, obtains α-different first
Base irisone crude product 150kg and dioxane aqueous solution 250kg, dioxane aqueous solution directly apply mechanically back reaction kettle.α-different
The rectifying at 1.0kPa, 130 DEG C of methylionone crude product, reflux ratio 4, obtains α-daphnone fine work 99.5kg.
Gas chromatographic analysis selectivity 99.3%, yield 99.5%, purity 99%.
Embodiment 3
The dioxane aqueous solution recycled in embodiment 2 and 50kg dioxane are added in 800L electrolytic cells, are electrolysed
Pond anode is Pt, and cathode is carbon-point.After opening stirring, 150kg pseudoisomethyl ionones are added into electrolytic cell.To electrode
15V voltages are passed through, react 1.5h at 20 DEG C of maintenance system.Electrolyte flashes at 25kPa, 64 DEG C, residence time 1min, obtain α-
Isomethylionone crude product 160kg and dioxane aqueous solution 240kg, dioxane aqueous solution directly apply mechanically back reaction kettle.
The rectifying at 1.4kPa, 150 DEG C of α-daphnone crude product, reflux ratio 5, obtains α-daphnone fine work
149.5kg.Gas chromatographic analysis selectivity 99.5%, yield 99.7%, purity 99.1%.
Embodiment 4
The dioxane aqueous solution recycled in embodiment 3 and 60kg water are added in 800L electrolytic cells, electrolytic cell anode
For Pt, cathode is carbon-point.After opening stirring, 150kg pseudoisomethyl ionones are added into electrolytic cell.It is passed through to electrode
25V voltages, react 2h at 30 DEG C of maintenance system.Electrolyte flashes at 30kPa, 70 DEG C, residence time 2min, obtains α-different methyl
Irisone crude product 165kg and dioxane aqueous solution 285kg, dioxane aqueous solution directly apply mechanically back reaction kettle.α-different first
The rectifying at 1.8kPa, 180 DEG C of base irisone crude product, reflux ratio 7, obtains α-daphnone fine work 148.5kg.Gas
Analysis of hplc selectivity 99.1%, yield 99%, purity 98.7%.
Embodiment 5
The dioxane aqueous solution recycled in embodiment 4 and 50kg dioxane are added in 800L electrolytic cells, are electrolysed
Pond anode is Pt, and cathode is carbon-point.After opening stirring, 200kg pseudoisomethyl ionones are added into electrolytic cell.To electrode
20V voltages are passed through, react 2h at 25 DEG C of maintenance system.Electrolyte flashes at 25kPa, 75 DEG C, residence time 1.5min, obtain α-
Isomethylionone crude product 170kg and dioxane aqueous solution 315kg, dioxane aqueous solution directly apply mechanically back reaction kettle.
The rectifying at 1.6kPa, 160 DEG C of α-daphnone crude product, reflux ratio 6, obtains α-daphnone fine work
148.5kg.Gas chromatographic analysis selectivity 99.1%, yield 99%, purity 98.7%.
Embodiment 6
1kg water and 1.5kg dioxane are added in 8L electrolytic cells, electrolytic cell anode Pt, cathode is carbon-point.Open
After stirring, 1kg (3E, 6Z)-fluoro- 3,6- dimethyl -3,6 of 10,10- bis-, 9- triens -2- are added into electrolytic cell
Ketone.15V voltages are passed through to electrode, react 1.5h at 20 DEG C of maintenance system.Electrolyte flashes at 25kPa, 64 DEG C, the residence time
1min, obtains (E) -4- (6,6- bis- fluoro- 2- methyl cyclohexanes -2- hexamethylene diamines-yl) -3- methyl-butyl- 3- hexamethylene diamine -2- ketone crude products
1.13kg and dioxane aqueous solution 2.29kg, dioxane aqueous solution directly apply mechanically back reaction kettle.(E) (6,6- bis- is fluoro- by -4-
2- methyl cyclohexanes -2- hexamethylene diamines-yl) -3- methyl-butyl- 3- hexamethylene diamine -2- ketone crude products rectifying at 1.4kPa, 150 DEG C, reflux
Than for 5, obtaining (E) -4- (6,6- bis- fluoro- 2- methyl cyclohexanes -2- hexamethylene diamines-yl) -3- methyl-butyl- 3- hexamethylene diamine -2- ketone
0.767kg.Gas chromatographic analysis selectivity 79.6%, yield 76.7%, purity 81.3%.
(E) -4- (the fluoro- 2- methyl cyclohexanes -2- hexamethylene diamines-yls of 6,6- bis-) -3- methyl-butyl- 3- hexamethylene diamine -2- ketone
1H-NMR(CDCl3,400MHz)：6.55ppm(1H, d, 6.2Hz), 5.37ppm (1H, d, 6.2Hz), 3.18 (1H,
Dt, 21Hz, 6.2Hz), 2.43ppm (3H, s), 2.27ppm (3H, s), 1.97ppm (2H, m), 1.92ppm (2H, m), 1.82ppm
(3H,s)。
m/z：214.12 (100.0%), 215.12 (13.2%)
Embodiment 7
1kg water and 1.5kg dioxane are added in 8L electrolytic cells, electrolytic cell anode Pt, cathode is carbon-point.Open
After stirring, 1kg (3E, 6Z) -8- cyclopropyl -3,6,10- trimethyls -3,6,9- triens -2- are added into electrolytic cell
Ketone.15V voltages are passed through to electrode, react 1.5h at 20 DEG C of maintenance system.Electrolyte flashes at 25kPa, 64 DEG C, the residence time
1min, obtains (E) -4- (4- cyclopropyl -2,6,6- 3-methyl cyclohexanols -2- hexamethylene diamines-yl) -3- methyl-butyl- 3- hexamethylene diamine -2- ketone
Crude product 1.09kg and dioxane aqueous solution 2.38kg, dioxane aqueous solution directly apply mechanically back reaction kettle.(E) -4- (4- rings third
Base -2,6,6- 3-methyl cyclohexanols -2- hexamethylene diamines-yl) -3- methyl-butyl- 3- hexamethylene diamine -2- ketone crude products are at 1.4kPa, 150 DEG C
Rectifying, reflux ratio 5, obtain (E) -4- (4- cyclopropyl -2,6,6- 3-methyl cyclohexanols -2- hexamethylene diamines-yl) -3- methyl-butyl- 3- oneself
Diamines -2- ketone 0.748kg.Gas chromatographic analysis selectivity 69.5%, yield 74.8%, purity 73.1%.
(E) -4- (4- cyclopropyl -2,6,6- 3-methyl cyclohexanols -2- hexamethylene diamines-yl) -3- methyl-butyl- 3- hexamethylene diamine -2- ketone
1H-NMR(CDCl3,400MHz)：6.55ppm(1H,d,5.25Hz),5.37ppm(1H,d,5.59Hz),2.62ppm
(1H,d,1.96Hz),2.43ppm(3H,s),2.27ppm(3H,s),1.94ppm(1H,m,1.96Hz),1.82ppm(3H,s),
1.66ppm(2H,m),0.99ppm(3H,s),0.24ppm(1H,m,0.22Hz),0.3ppm(2H,m)
m/z：246.20 (100.0%), 247.20 (18.7%), 248.21 (1.7%).
Claims (14)
1. a kind of method of cyclization, including the method that compound shown in formula (I) passes through compound shown in electrolytic preparation formula (II)：
Wherein, R1、R2、R3、R4Mutually independent expression H, halogen, aryl, C1~C6Straight or branched alkyl, C3~C6Cycloalkyl；
R5Selected from H or cyclopropyl.
2. the according to the method described in claim 1, it is characterized in that, R1、R2、R3、R4Mutually independent expression methyl, F.
3. according to the method described in claim 1, it is characterized in that, the temperature of the electrolysis is 10 DEG C~30 DEG C.
4. according to the method described in claim 3, it is characterized in that, the temperature of the electrolysis is 18 DEG C~22 DEG C.
5. according to the method described in claim 1, it is characterized in that, the electrode potential of the electrolysis is 5V~25V.
6. according to the method described in claim 5, it is characterized in that, the electrode potential of the electrolysis is 12V~18V.
7. according to the method described in claim 1, it is characterized in that, the reaction time of the electrolysis is 1~3h.
8. the method according to the description of claim 7 is characterized in that the reaction time of the electrolysis is 1.4~1.6h.
9. according to the method described in claim 1, it is characterized in that, the cathode of the electrolysis is carbon-point, the anode of the electrolysis
For Cu, Ag or Pt.
10. according to the method described in claim 1, it is characterized in that, the electrolyte of the electrolysis contains organic solvent and water, institute
State organic solvent and be selected from dioxane or tetrahydrofuran.
11. according to the method described in claim 10, it is characterized in that, compound shown in formula (I)：Organic solvent：H2The quality of O
Than for (2~6)：(2~4)：(1~3).
12. according to the method described in claim 1, it is characterized in that, compound shown in formula (I) is selected from following compound：
A kind of 13. method of electrolytic preparation α-daphnone, it is characterised in that use organic solvent and H2O is as electrolysis
Liquid, pseudoisomethyl iononeElectrolytic preparation α-daphnone
Cathode is carbon-point, anode Cu, Ag or Pt；Electrolysis temperature is 10 DEG C~30 DEG C；Electrode potential is 5V~25V；During cell reaction
Between be 1~3h；Pseudoisomethyl ionone：Organic solvent：H2The mass ratio of O is (2~6)：(2~4)：(1~3)；It is described
Organic solvent be selected from dioxane or tetrahydrofuran.
14. according to the method for claim 13, it is characterised in that the electrolysis temperature is 18 DEG C~22 DEG C；Electrode potential
For 12V~18V；The cell reaction time is 1.4~1.6h.
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